Flame retardant materials

ABSTRACT

New flame retardant materials are disclosed having applied thereon compounds of the formula:   WHEREIN R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms, X is selected from the group consisting of chlorine, bromine and lower alkyl of 1-6 carbon atoms, m is an integer from 1-4 and n is an integer from 0-5, provided that the sum of m and n is not greater than 6 and when m is 1, n is greater than 0.

United States Patent Golborn et al.

FLAME RETARDANT MATERIALS Inventors: Peter Golborn, Lewiston; James J.

Duffy, Buffalo, both of NY.

Assignee: Hooker Chemical & Plastics Corporation, Niagara Falls, NY.

Filed: Sept. 4, 1973 Appl. No.: 393,868

Related US. Application Data Division of Ser. No. 239,784.

US. Cl. 428/289; 428/288; 428/378; 428/921 Int. Cl C09d 5/18 Field of Search 117/136, 138.8 B, 143 R, 117/144, 154, 141; 260/932 References Cited UNITED STATES PATENTS l/l954 Ferguson 117/136 X 8/1957 Erbel et al. 117/136 l/1959 Fon Toy et al. 117/136 [4 1 July 15,1975

Primary ExaminerRa1ph Husack Assistant Examiner-Theodore G. Davis Attorney, Agent, or Firm-Peter F. Casella; Donald C. Studley; William J. Crossetta, Jr.

[5 7] ABSTRACT New flame retardant materials are disclosed having applied thereon compounds of the formula:

(no) 2 P CHZNHC 19 Claims, No Drawings 1 FLAME RETARDANT MATERIALS This is a division of application Ser. No. 239,784, filed Mar. 30, 1972, now US Pat. No. 3,803,269 issued Apr. 9, 1974.

FIELD OF INVENTION This invention relates to novel compounds of the formula R0 P CH LHC wherein R is selected from the group consisting of phenyl, lower altenly, and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms, X is selected from the group consisting of chlorine, bromide and lower alkyl of 1-6 carbon atoms, m is an integer from l-4and n is an integer from O-5, provided that the sum of m and n is not greater than 6 and when m is l, X is greater than 0. The invention includes methods of applying the above novel compounds to normally flammable textiles, thermoplastic, thermosetting, and elastomeric resin compositions so as to render them flame retardant.

BACKGROUND OF THE INVENTION Many flame retarding agents and methods of application have been developed in attempts to obtain flame resistant textile materials and thermoplastic, thermosetting, and elastomeric resin compositions.

Flame retardant textiles have been produced by depositing metal oxides, within or on the textile fibers, by the successive precipitation of ferric oxides and a mixture of tungstic acid and stannic oxide or by successive deposition of antimony trioxide and titanium dioxide.

Such processes require plural treatment baths in which strongly acidic solutions are employed thus posing the problem of possible textile degradation. Furthermore, metal oxide coatings on textile materials create difficulties in subsequen dyeing processes which deleteriously affect the hand of the finished product. Another process involves the use of a single processing bath wherein a dispersion of a chlorinated hydrocarbon and finely divided antimony oxide is padded on the textile material. Near the textile combustion temperature antimony oxide will react with hydrogen chloride, generated by degradation of the chlorinated hydrocarbon, to form antimony oxychloride which acts to suppress flame. This combination of a chlorinated hydrocarbon and finely divided antimony oxide are not acceptable finishes for closely woven textiles as they deleteriously affect the hand of the finished product. A further process for imparting flame resistance to cellulosic materials is by the esterification of the cellulose with diammonium hydrogen orthophosphate. Textile products so treated however are subjected to metathesis reaction with cations during washing, and must be regenerated by reacting the wash product with an ammonium chloride solution.

The production of thermoplastic, thermosetting, and elastomeric resin compositions which are flame retardant is of considerable commercial importance. For example, such articles as castings, moldings, foamed or laminated scructures and the like are required, or are at least desired, to be resistant to fire and flame and to possess the ability to endure heat without deterioration. The use of various materials incorporated into thermoplastic, thermosetting and elastomeric resins so as to improve the flame retardancy thereof has been known. Many compounds have been commercially available for such use, among them being chlorostyrene copolymers, chlorinated paraffin wax in admixture with triphenyl styrene, chlorinated paraffins and aliphatic antimonical compounds, as well as antimony oxidechlorinated hydrocarbon mixtures. A problem associated with these compounds has been however, the fact that generally a large amount, i.e. upwards of 35% of additive, must be incorporated into the resin in order to make it sufficiently flame retardant. Such large amounts of addative may deliteriously affect the physical characteristics of the thermoplastic resin, as well as substantially complicating and increasing the cost of preparation thereof. A further problem is that these prior art additives tend to crystallize or oil out of the resin after a relatively short time of incorporation. The present invention relates to a group of compounds which may be added to thermoplastic resins in relatively small amounts and still produce satisfactory flame retardant compositions which will not crystallize nor oil out of the resin after incorporation therein.

OBJECTS OF THE INVENTION It is, therefore, a principal object of this invention to provide novel compounds of the formula:

o n (no P CHZHHC- wherein R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of l-6 carbon atoms, X is selected from the group consisting of chlorine, bromine and lower alkyl of l-6 carbon atoms, m is an integer from I-4 and n is an integer from 0-5, provided that the sum of m and n is not greater than 6 and when m is 1, X is greater than 0.

It is also an object of this invention to provide flame retarding textile materials comprising normally flammable cellulosic, proteinaceous or analogous manmade materials. Another object is to provide a method for treating normally flammable cellulosic, proteinaceous or analogous manmade materials to render them flame retardant. Another object is to provide flame retarding thermoplstic, thermosetting or elastomeric resin compositions comprising normally flammable resin materials. A further object is to provide a process for treating normally flammable thermoplastic, thermosetting or elastomeric resin compositions to render them flame retardant. A particular object is to devise a composition comprising normally flammable cellulosic, proteinaceous or analogous man-made materials and an effective flame retardant amount of the compound represented by the formula wherein R, X, m and n are as above described.

A further particular object is to devise a composition comprising normally flammable thermoplastic, thermosetting or elastomeric polymers and an effective flame retarding amount of the before described novel compound.

These and other objects of the present invention will be obvious from the following description.

DESCRIPTION OF THE INVENTION In accordance with this invention there are provided novel compounds, for imparting flame retardancy to textiles and resin materials, of the formula More specifically, the preferred compounds of the present invention include these compounds wherein R is lower alkyl, alkenyl chlorinated alkyl or phenyl, and X is chlorine, bromine or methyl.

Illustrative examples of compounds of the present invention include, for instance, compounds of the general formula such as Br BrO O D 0 O This synthesis of the compositions of the present ina suitable solvent, excess of the phosphite or neat. Typically, the reaction occurs at elevated temperatures and is continued for about 1 to about 12 hours. Temperatures are generally about C to about 160C. Preferably reaction is continued from about 3 to about 6 hours at a temperature of about 80C to about 120C. The solvent or other volatiles is thereafter stripped, or otherwise removed from the product. Suitable solvents include benzene, toluene, xylene, glymes, dimethylformamide, aliphatic or aromatic hydrocarbons. Typical N- hydroxymethyl aromatic amides operable as reactants herein include P. P. HOCH NHuGNHCH OH Br 9. c1 cuacu on o I c uucu ou 5- to cl- 0 CNHCHZOH i gnua-l ou 1 l o o HOCH HNE gm- OH fir 0 2 \K\/ 2 ll o o Cl- 0 -cm-lcu ou HOCHZHNC E Z One or more of the novel compounds of this invention may be applied to textile materials by conventional finishing techniques such as by thermal induced pad curing so as to incorporate into the textile a flame retardant amount thereof. The compounds of this invention have advantages over the flame retardant agents of the prior art in that they may be used on a variety of textile materials of different chemical composition, and

they may be applied by a variety of methods. They may be applied to materials in either the fiber or fabric form to give flame retarding materials with minimum detectable physical changes in the quality or hand of the textile material.

Cellulosic textile materials may be made flame retardant by way of a variety of methods. Products of this invention may be applied to cellulosic materials in several ways to give a durable flame retardant treatment. For example, the products of this invention may be reacted with formaldehyde to give N-hydroxymethyl derivatives which can react with cellulosic materials in a known manner. Alternatively aqueous mixtures of the products with formaldehyde, urea, trimethylol melamine or other known cellulose crosslinking agents may be applied to a cellulose substrated with the aid of an acidic catalyst by a pad dry process.

More preferably the N-hydroxymethyl derivative of the products of this invention prepared by the condensation of the products with formaldehyde, are mixed in an aqueous medium with trimethylol melamine and a Lewis acid catalyst such as NH Cl or Zn(NO .6H O. The cellulosic material is immersed in a aqueous solution of the methyl derivative, trimethylol melamine, and Zn(NO .6H O and squeezed on a two roll padder to -90% wet weight pick-up. The material is dried at 220-270F for l-3 minutes and cured at 300-370F for l-6 minutes in a circulating air oven. The samples are then washed in hot water and dried. The finished samples have a flame retardant add on of about 5 to about 40% and preferably about 10 to about 25% by weight.

The flame retardant agents of this invention may be applied to various textiles such as cellulosic materials, proteinaceous materials and blends of cellulosic or proteinaceous materials and analogous manmade fibers. By cellulosic materials, applicant intends to embrace cotton, ravon, paper, regenerated cellulose and cellulose derivatives which retain a cellulose backbone of at least one hydroxy substituent per repeating glucose unit. By proteinaceous material applicant intends to embrace those textile materials comprising the functional groups of proteins such as the various animal wools, hairs and furs.

The flame retardant compounds or additives of the invention may be incorporated into thermoplastic, thermosetting or elastomeric resin compositions by any known method. That is to say, the flame retardant additive may be added to the resin by milling the resin and the additive on, for example, a two-roll mill, or in a Banbury mixer etc., or it may be added by molding or extruding the additive and resin simultaneously, or by merely blending it with the resin in powder form and thereafter forming the desired article. Additionally, the flame-retardant may be added during the resin manufacture, i.e., during the polymerization procedure by which the resin is made, provided the catalysts etc. and

other ingredients of the polymerization system are inert v Suitable monomers are ethylene, propylene, butene, pentene, hexene, heptene, octene, 2-methylpropene-l, 3-methylbutenel 4-methylpentenel 4-methylhexenel ,S-methylhexene-l bicyclo-(2.2.1 )-2- heptene, butadiene, pentadiene, hexadiene, isoprene, 2,3-dimethylbutadiene-l ,3, Z-methylpentadiene-l ,3, 4-vinylcyclohexene, vinylcyclohexene, cyclopentadiene, styrene and methylstyrene, and the like.

Other polymers in addition to the above-described olefin polymers that are useful in the invention include polyindene, indenecoumarone resins; polymers of acrylate esters and polymers of methacrylate esters, any late and methacrylate resins such as ethyl acrylate, nbutyl methacrylate, isobutyl methacrylate, ethyl methacrylate and methyl methacrylate; alkyd resins and paint vehicles, such as bodied linseed oil; cellulose derivatives such as cellulose acetate, cellulose acetate butyrate, cellulose nitrate, ethyl cellulose, hydroxyethyl cellulose, methyl cellulose and sodium carboxymethyl cellulose; epoxy resins; furan resins (furfuryl alcohol or furfuralketone); hydrocarbon resins from petroleum; isobutylene resins (polyisobutylene); isocyanate resins (polyurethanes); melamine resins such as melamineformaldehyde and melamine-urea-formaldehyde; oleoresins; phenolic resins such as phenol-formaldehyde, phenolic-elastomer, phenolic-epoxy, phenolicpolyamide, and phenolic-vinyl acetals; polyamide polymers, such as polyamides, polyamide-epoxy and particularly long chain synthetic polymeric amides containing recurring carbonamide groups as an integral part of the main polymer chain; polyester resins such as unsaturated polyesters of dibasic acids and dihydroxy compounds, and polyester elastomer and resorcinol resins such as resorcinol-formaldehyde, resorcinol-furfural, resorcinol-phenol-formaldehyde, resorcinol-polyamide and resorcinol-urea; rubbers such as natural rubber, synthetic polyisoprene, reclaimed rubber, chlorinated rubber, polybutadiene, cyclized rubber, butadieneacrylonitrile rubber, butadiene-styrene rubber, and butyl rubber; neoprene rubber (polychloroprene); polysulfides (Thiokol); terpene resins; urea resins; vinyl resins such as polymers of vinyl acetal, vinyl acetate or vinyl alcohol-acetate copolymer, vinyl alcohol,

vinyl chloride, vinly butyral, vinyl chloride-acetate copolymer, vinyl pyrrolidone and vinylidene chloride copolymers; polyformaldehyde; polyphenylene oxide; polymers of diallyl phthalates and phthalates; polycarbonates of phosgene or thiophosgene and dihydroxy compounds such as bisphenols phosgene, thermoplastic polymers of bisphenols and epichlorohydrin (trade named Phenoxy polymers); graft copolymers and polymers of unsaturated hydrocarbons and unsaturated monomer, such as graft copolymers of polybutadiene, styrene and acrylonitrile, commonly called ABS resins; ABS polyvinyl chloride polymers, recently introduced under the trade name of Cycovin; and acrylic polyvinyl chloride polymers, known by the trade name Kydex 100.

The polymers of the invention can be in various physical forms, such as shaped articles, for example, moldings, sheets, rods, and the like; fibers, coatings, films and fabrics, and the like.

The compounds of this invention have been found to have particular utility in ABS resins and in elastomeric materials such as acrylic rubber; acrylonitrilebutadiene styrene terpolymers; butadiene-acrylonitrile copolymers; butyl rubber; chlorinated rubbers, e.g., polyvinyl chloride resins, chloroprene rubber, chlorosulfonated polyethylene; ethylene polymers, e.g., ethylene-propylene copolymers, ethylene-propylene terpolymers; fluorinated rubbers, butadiene rubbers, e.g., styrene-butadiene rubber, isobutylene polymers, polybutadiene polymers, polyisobutylene rubbers, polyisoprene rubbers; polysulfide rubbers; silicon rubbers; urethane rubbers; high styrene resins latices, high sty rene resins, vinyl resins; sponge rubber; and the like.

It should be noted that it is also within the scope of the present invention to incorporate such ingredients as plasticizers, dyes, pigments, stabilizers, antioxidants, antistatic agents and the like to the novel composition.

ASTM Test D2863-70, used in accordance with the following examples, generally provides for the comparison of relative flammability of self-supporting plastics by measuring the minimum concentration of oxygen in a slowly rising mixture of oxygen and nitrogen that will support combustion. The procedure encompasses supporting cylindrical test specimens -150 mm X 8.0 mm vertically in a glass tube fitted with controlled upward oxygen-nitrogen gas flow. The top of the specimen is ignited and oxygen flow is adjusted until it reaches that minimum rate at which the specimen is extinguished before burning 3 minutes or 50 mm whichever happens first. The oxygen index(n) is then calculated as follows:

wherein O is the volumetric flow of oxygen, at the minimal rate and N is the corresponding volumetric flow rate of nitrogen.

A modification of ASTM Test D635-68 used in accordance with the following'examples, generally provides for the comparison of burning rates, selfextinguishment and non-burning characteristics of plastics in the form of sheets, bars, plates or panels. The

procedure encompasses preparing plastic samples of 1 -200 mm X 8 mm with and without the subject flame additive. Each sample is marked at points 1 inch and 4 inches from its end and held, marked end in the flame, at a 45 angle in a controlled burner flame (1 inch flame length) for two 30 second attempts. The movement of the flame up the length of the sample through the two points is measured for rate of burning. non-burning or self-extinguishing characteristics. A sample is rated SE(self-extinguishing) if the flame burns through the first point but extinguishes before reaching the second point. A sample is rated NB(nonburning) if, upon ignition it does not burn to the first point.

AATCC test method 34-1969, The Vertical Char Test, used in accordance with the following examples, generally provides for the comparison of relative flammability of 2% inch X 10 inch fabric test specimens when exposed to a controlled burner flame, under controlled conditions, for periods of 12.0 and 3.0 seconds. Charred specimens are thereafter subjected to control tearing tests, using tabulated weights, to determine the average tear length as representing the char length of the fabric. In addition, samples which are wholly consumed by the flame are rated (B) and samples which do not burn are rated (NB). For comparison purposes, it should be noted that untreated samples of the fabrics used in the examples of this case would be consumed for this test.

In all the examples of the application, the following general procedure was used except when otherwise specifically noted. Padding was done on a standard two EXAMPLE 1 Preparation of A 500 ml. flask was changed with 124g. (1.0 mole) of trimethyl phosphite and was heated to about 100C. 57.5g. (0.25 mole) of 3-bromo-N-hydroxymethyl benzamide was then added to the reaction flask over a period of minutes. The reaction mixture was then refluxed at about 95 for about 3 hours then stripped at 100C under a vacuum of 0.5 mm mercury to give 81g of a colorless, viscous oil which by elemental analysis was confirmed to be the desired product.

EXAMPLE 11 Preparation of Following the procedure described in Example I 69g. (0.3 mole) of 3-bromo-N-hydroxymethyl benzamide was refluxed with 80g. (0.35 mole) of tri-n-butyl phosphite for about 5 hours at about 125C. n-Butanol and excess tri-n-butyl phosphite were removed by stripping the reaction mixture at 1 C under a vacuum of 0.5 mm mercury. After stripping 121g. of a pale yellow viscous liquid was obtained which was confirmed, by elemental analysis to be the desired product.

EXAMPLE "I Preparation of A 500 ml. flask, fitted with a reflux condenser, mechanical stirrer and thermometer, was charged with 124g. 1.0 mole) of trimethyl phosphite and was heated to about 100C. 61.8g. (0.3 mole) of 2,4-dichloro-N- hydroxymethyl benzamide was added to the trimethyl phosphite, over a period of about 5 minutes. The homogeneous reaction mixture was then refluxed at about 93C for 3 hours and thereafter stripped, under a reduced pressure of about 0.5 mm Hg. at about 10C, to give 93g. ofa tacky solid. Recrystallization of the solid from benzene of cyclohexane (1:1) gave 828g. of dimethyl 2,4-dichlorobenzamidomethyl phosphonate.

EXAMPLE 1V 5 Preparation of c1 ct A 250 ml. flask was charged with 62g. (0.5 mole) of trimethyl phosphite and was heated to about 100C. 29g. (0.1 mole) of bis-N,N-hydroxymethyl tetrachloroterephthalamide was added to the flask and the reaction mixture was refluxed for about 6 hours and then cooled to room temperature. Unreacted solids were filtered off and the filtrate was stripped, at 70C under 2 mm. mercury of reduced pressure, to give 12.0g. of a tacky solid product which was found, by infrared and nuclear magnetic resonance spectroscopy to be substantially pure desired product.

EXAMPLE V Preparation of 0 y o CNHCH P(OCH CH Cl) A 250 ml. flask was charged with 21.9g. (0.1 mole) of 2,4-dichloro-N-hydroxymethyl benzamide and 27g. (0.1 mole) of tris-2-chloroethyl phosphite. This reaction mixture was heated at about 130C for about 4 hours then stripped, at 100C under a vacuum of 1.3 mm mercury, to give 41 grams of a white solid. The product was proven, by elemental and infrared and nu clear magnetic resonance spectroscopy, to be substan tially pure desired product.

EXAMPLE VI Preparation of 0 0 45 ll ll CNHCH2P(OCH?CH-CH2)2 A 250 ml. flask was charged with 16.5g. (0.1 mole) of N-hydroxymethyl-p-toluamide and 40.2g. (0.2 mole) of triallyl phosphite and this reaction mixture was heated at about 130C for about 4 hours. Excess triallyl phosphite and allyl alcohol were removed by stripping, at 100C under a vacuum of 2 mm mercury, to yield a thick yellow oil product. The product was confirmed by infrared and nuclear magnetic resonance spectroscopy and elemental analyses.

EXAMPLE V11 Preparation of CMlCH P(0CH A 500 ml. flask, equipped with mechanical stirrer, thermometer and reflux condenser, was charged with 66g (0.4 mole) of N-hydroxymethyl p-toluamide and 124 g (1.0 mole of trimethyl phosphite. This reaction mixture was refluxed for about 4 hours then stripped, at 70C under 0.2 mm mercury vacuum, to give 95g of a low melting solid. Elemental analysis with infrared and nuclear magnetic resonance spectroscopy confirmed the structure of the product.

EXAMPLE VIII Preparation of EXAMPLE IX Preparation of A mixture of 44.8g (0.2 mole) of N,N'-bishydroxyphenyl terephthalamide and 124 g (1.0 mole) of trimethyl phosphite was refluxed for about 6 hours. After the completion of the reaction the mixture was stripped, at 120C and 1 mm Hg, to remove excess phosphite and other volatiles. The product was confirmed by infrared and nuclearmagnetic resonance spectroscopy.

atile materials. A yellow liquid, which weighed 62.0g, was isolated and confirmed as the desired product by spectroscopic and elemental analyses.

EXAMPLE XI Forty parts of N-dimethylphosphenomethyl-Z,4- dichlorobenzamide was mixed with parts of polypropylene and dry blended for about five minutes. This mixture was then heated to a melt and mixed well in the molten state for about 15 minutes. The mixture was then allowed to cool to room temperature and the plastic composition was cut into small pieces. These pieces were placed slowly into a glass tube (9 mm) immersed in a hot metal bath, the temperature of the bath being maintained above the melt temperature of the plastic composition. Pieces of the composition were added until the melt had a depth of approximately 200 mm. A metal rod was then placed in the tube with a weight attached and the tube cooled to'solidify the composition. The composition was then removed from the tube and tested by ASTM tests D2863- and D635-68. The results of the testing are contained in Table l.

EXAMPLES XII-XXIX Various additive compounds were mixed and treated with various resins according to the method of Example XI. Table l tabulates the results of testing by ASTM tests D2863-70 and D635-68 for Examples XII-XXIX.

EXAMPLE XXX N-Dimethyl phosphonomethyl-p-toluamide (25g) was mixed with 40% formalin solution (37.5g) and stirred overnight at pH 10. The pH was adjusted to 7.0 with hydrochloric acid and 3. lg of ammonium chloride and 14.0g of a 50% solution of a methylolated melamine added. 5.0 oz. sq. yd. cotton sheeting was immersed in the solution and the excess squeezed from the cloth by passing through a two roll laboratory padder at 60 lb. gauge pressure, to a wet pick-up of about The sheeting was then dried at about 250F for about 2 minutes and cured at about 340F for about 5 minutes in a circulating air oven. The sheeting was then washed by hand for about 5 minutes in a detergent EXAMPLE X (Tide) water mixture and tumble dried. A resin pick-up Prepfl UOfl 0f 55 of 23.7% was calculated.

r A a l. t I ercent Flafl-nabi Ii ty Tests Example Polymer Additive wa Q; 3. 35

O 0 II II x1 Polypropylene cl @-c. ll-lcli l (ocll 19- SE 9. 9. xx! Nylon @CNHCH2P(0CH3)2 30 26.6 NB

9. 9 I XIII Polyethylene @CNHCH P(OCH O 28 NB Tcrcphthalate 2 3 2 3 T A B L E I-Continued Fle -ability mt-ts Examnlc Polymer Additive Q; 3.535

9. 9. XIV ASS CNHCH2P(0CH3)2 30 2h NB XV Nylon ditto 3O 25 N8 XVI Polyethylene ditto 3O 36 NB Terephthalate 9. P. XVI! Ass CNHCt-l P(OCH CH CH CH +0 22.3 $5

xvtn Nylon g ditto 26 NB XIX Epoxy ditto 3O 29 NB 9. 9. XX st rene CH @-CNHCH P(0CH 30 23.3 SE

T A B L E (continued) Pderpqnt Flammability Tests Example Polymer Additive il E Fn 01 -5 0 0 II II XXI Polyethylene CH -@-CNHGl P(OCl-l CH=Cl-l '40 29A NB Terephthalate P. P. 'xxu Epoxy CHJ-@-CNHG-I P-(O-@)2 3 SE o o o 0 II II I II xxnx Epoxy (H cO )PcH HNC-@-CNrio-i P(0cH 30 28 SE XXIV Polyethylene ditto 3 7-5 Terephthalate xxv ABS ditto E P. 9. 9. 9. xxv: Polystyrene (H C=CHCH 0)PCH HNC-@-CNHCl-l P(0Cl-l CH=CH b0 SE xxvzt Ass ditto 30 2 4-3 9. 9. xxvm Polystyrene Cl-@ C-NHCH HOCH CH CU no 23- xxtx ssa ditto 30 2 4.1 SE

test 34-1969.

EXAMPLES XXXI-XXXlll Using the method of Example 30, 5 oz. per sq. yard cotton sheeting was treated with various compounds and subjected to ASTM test D2863-70 and AATCC test 34-1969. The results therefore are indicated in Table 11.

EXAMPLE XXXIV Rayon staple fiber was immersed in the solution described in Example XXX and squeezed on a two roll laboratory padder at about 60 lb. gauge pressure to a wet pick-up of about The fiber was then dried for about 3 minutes at about 250F and cured for about 10 minites at about 350F in a circulating air oven. The fiber was then washed by hand for about 5 minutes in a hot detergent (Tide) water mixture and dried in the circulating air oven resulting in an add-on of about 13.8%. The fiber was then tested for flammability by holding one end of a treated sample in a benson flame for about 2 sec. and then removing and observing the sample. Treated samples self-extinguish immediately while untreated samples are completely consumed.

The fiber was then further tested for durability by We claim: y

l. A fire retardant textile material comprising a textile selected from-the group consisting of cellulosic fibers proteinaceous fibers and blends thereof and a SubjeCtlng it to a Complete Wash cycles in a Standard, 5 flame retardant amount of a compound of the formula: home type automatic washer using Tide detergent. Thereafter the fiber was tested for flammability as previously described. The results of testing is tabulated in X 0 ,0 r1 Table 11. I

EXAMPLES XXXV-XXXVI P CHZNHC Using the method of Example XXXlV, rayon staple m fiber was treated with various compounds and sub jected to ASTM test D2863-7O and AATCC test 34-1969. The results are shown in Table I1.

wherein R is selected from the group consisting of phe- EXAMPLE XXXVH my], lower alkenyl and halogen substituted and unsub- N-Diallyl phosphonomethyl-p-toluam d g) was stituted lower alkyl of 1-6 carbon atoms, X is selected m d with 40% formalin Solution g) and Stirred from the group consisting of chlorine, bromine and overnight at pH 10. The pH was brought to 7.0 with hy-' lower alkyl of 1-6 carbon atoms, m is an integer from dr ChI C a nd ammonium g) and a and n is an integer from O5, provided that the sum 50% Solution Of a methylolated mfllamine g) of m and n is not greater than 6 and when m is l, X is added. greater than 0.

6.0 02. sq. yd. wool was immersed in the above solu- 2. The textile material of claim 1 wherein said textile tion. squeezed on a 2 roll laboratory padder to a wet is a blend of cellulosic and proteinaceous fibers. pick-up of about 100% dried for about 2 minutes at 3. The textile material of claim 1 wherein said textile about 250F and cured for about 5 minutes at about is 66111110516 fibers- 350F in a circulating air oven. The was h 4. The textile material of claim 1 wherein said comwashed for one wash cycle using Tide, in a standard, Pound is? home type, automatic washer and tumble dried. Theresin add-on was calculated as 25.3%. 0 0

The thus treated wool was thereafter subjected to ASTM test D2863-70 and AATCC test 34-1969. The CNll(.l-l P(0Cl-l wool was then subjected to four additional one cycle 35 l washings in a standard home type automatic washer, as above described, and thereafter tested by AATCC test 34-1969. Test results are tabulated in Table 11. r

- T A I 1. E 11 T I 3 l i 7 "ram: 1 V l EXI' 'TI'. futile Add-on In tial Jalflal mm I 0 -0 g xxx cm. (s n.) cn,-@ cmn vtm,) 2 1 1 xxx! 111m .@-CI1O P(0Cfl 5 27- 1.0 3.1 v 1 11 9. 1. xxxtt ditto (11 co )rc11 1mc-@-cmu1 r(ccn 20.2 21. m 5.0 xxxnr ditto mic i 18.6 is I i xxxzv 11 m (staple) m -@-cmu1 r(uc11 1 I 13.5 s: s;

xxxv m:- .tca ql-cu n rcu mccmas rtaa uwuqp 19.13v 12.7 s: st

xxxvt am." am. I l i 18.9 a I 5. The textile material of claim 1 wherein said com- 10. The textile material of claim 1 wherein said compound is: pound is:

0 o o [in S 'I '7 CNHCl-l P OCH cNncn P(ocH cn cH cH 2 3 CH3 6. The textile material of claim 1 wherein said compound is:

11. The textile material of claim 1 wherein said com- 9 H pound is: I 2 3 )2 O 0 C CNHCH P- o 7. The textile material of claim 1 wherein said com- 3 pound'is: 12. The textile material of claim 1 wherein said compound is:

9 o 0 0' (H3C0)2PCH2HN' 1 v1 'r v H CO PCH NHC CNHCH P OCH Thefextile material of claim 1 wherein Said 13. The textile material of claim 1 wherein said compound pound is:

14. The fire retardant textile material of claim 1 HCHZHQCHZCH=CHZ )2 wherein about 5 to about 40% by weight of said compound has been added on.

15. The fire retardant textile material of claim 1 wherein about 10 to about 25% by weight of said compound has been added on.

3 16. The fire retardant textile material of claim 1 wherein said compound is applied by padding.

9. The textile material of claim 1 wherein said com- The fire retardant textile material of claim 1 Pound is? wherein said compound is applied to thermal induced R R pad curing.

NHCH P(OCH CH C1) 18. The fire retardant textile material of claim 1 1 wherein said compound is applied to the textile material while in the fiber form.

19. The fire retardant textile material of claim 1 wherein said compound is applied to the textile mate rial in fabric form. 

1. A FIRE RETARDANT TEXTILE MATERIAL COMPRISING A TEXTILE SELECTED FROM THE GORUP CONSISTING OF CELLULOSIC FIBERS PROTEINACEOUS FIBERS AND BLEND THEREOF AND A FLAME RETARDANT AMOUNT OF A COMPOUND OF THE FORMULA:
 2. The textile material of claim 1 wherein said textile is a blend of cellulosic and proteinaceous fibers.
 3. The textile material of claim 1 wherein said textile is cellulosic fibers.
 4. The textile material of claim 1 wherein said compound is:
 5. The textile material of claim 1 wherein said compound is:
 6. The textile material of claim 1 wherein said compound is:
 7. The textile material of claim 1 wherein said compound is:
 8. The textile material of claim 1 wherein said compound is:
 9. The textile material of claim 1 wherein said compound is:
 10. The textile material of claim 1 wherein said compound is:
 11. The textile material of claim 1 wherein said compound is:
 12. The textile material of claim 1 wherein said compound is:
 13. The textile material of claim 1 wherein said compound is:
 14. The fire retardant textile material of claim 1 wherein about 5 to about 40% by weight of said compound has been added on.
 15. The fire retardant textile material of claim 1 wherein about 10 to about 25% by weight of said compound has been added on.
 16. The fire retardant textile material of claim 1 wherein said compound is applied by padding.
 17. The fire retardant textile material of claim 1 wherein said compound is applied to thermal induced pad curing.
 18. The fire retardant textile material of claim 1 wherein said compound is applied to the textile material while in the fiber form.
 19. The fire retardant textile material of claim 1 wherein said compound is applied to the textile material in fabric form. 